It is located in the White Mountains, and part of the White Mountain National Forest is in the south. Shelburne is home to Leadmine State Forest. The Appalachian Trail crosses the town.

First granted in 1769 by Governor John Wentworth, the town was named for William Petty Fitzmaurice, Earl of Shelburne. He was a supporter of independence for the American colonies, and at his insistence, King George III recognized the independence of the United States. The town was first settled in 1771, and incorporated on December 13, 1820, when Shelburne voters chose to keep the name. It included Shelburne Addition until that was set off and incorporated in 1836 as Gorham.

According to the US census, the town has a total area of 48.8 square miles, of which 47.9 sq mi is land and 0.9 sq mi is water, comprising 1.84% of the town. Shelburne is drained by the Androscoggin River. Part of the Mahoosuc Range is in the north, while the northern end of the Carter-Moriah Range is to the south.

As of the 2010 census, there were 372 people residing in the town, and according to the 2000 census there were 156 households, and 114 families residing in the town. The population density was 7.9 people per square mile. There were 197 housing units at an average density of 4.1 per square mile.

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